1:2-chromium complexes of a monoazo dyestuff and a disazo dyestuff

ABSTRACT

Fiber-reactive 1:2-chromium complex compounds containing one atom of metal linked in complex union with a monoazo dyestuff molecule and with a disazo dyestuff molecule containing the grouping   IN WHICH N 1 OR 2, AND WHICH FURTHER CONTAIN ONE OR SEVERAL FIBER-REACTIVE GROUPINGS ARE SUITABLE FOR DYEING OR PRINTING WOOL, SILK, SUPERPOLYAMIDE FIBERS, AND POLYHYDROXYLATED FIBROUS STRUCTURES SUCH AS REGENERATED CELLULOSE AND VISCOSE FIBERS, LINEN AND COTTON. The resulting dyeings are even and have good fastness to light, washing, fulling, decatizing, carbonizing and abrasion. The new dyes are valuable to obtain neutral grey and black tints.

Unite States Patent Inventors Gerhard Back Loerrach, Germany; Hans Ulrich Schuetz, Basel, Switzerland [21] Appl. No. 734,525 [22] Filed June 5,1968 [45] Patented Dec. 7, 1971 [73] Assignee Ciba Limited Basel, Switzerland [32] Priority June 9, 1968 [3 3] Switzerland [31] 8224/67 [54] 1:2-Cl-1ROMIUM COMPLEXES OF A MONOAZO DYESTUFF AND A DISAZO DYESTUFF 8 Claims, No Drawings [52] 111.8.(31 260/145 A, 8/4, 8/42, 8/71, 1l7/l38.8, 117/144, 260/37, 260/145 B, 260/146 T, 260/151, 260/160, 260/185, 260/191, 260/195 [51] Int. Cl 3 096 45/06, 006p 1/10 [50] Field of Search 260/145 A, 1 145 B [56] References Cited UNITED STATES PATENTS 2,933,488 4/1960 Biedermann et a1 260/145 2,933,489 4/1960 Biedermann et a1 260/145 2,933,490 4/1960 Biedermann et all... 260/145 3,040,019 6/1962 Neier 260/145 3,412,081 11/1968 Ackermann 260/145 Primary Examiner-Floyd D, Higel Attorneys-Harry Goldsmith, Joseph G. Kolodny, Bryant W.

Brennan and Edward J. Sites in which n=1 or 2, and which further contain one or several fiber-reactive groupings are suitable for dyeing or printing wool, silk, superpolyamide fibers, and polyhydroxylated fibrous structures such as regenerated cellulose and viscose fibers, linen and cotton. The resulting dyeings are even andhave good fastness to light, washing, fulling, decatizing, carbonizing and abrasion. The new dyes are valuable to obtain neutral grey and black tints.

l:2-CHROMIUM COMPLEXES OF A MONOAZO IDYESTUFF AND A DlSAZO DYESTUFF The present invention provides fiber-reactive lz2-chromium complex compounds containing one atom of metal linked in complex union with a monoazo dyestuff molecule and with a disazo dyestuff molecule containing the grouping (SOaIzDu n=1 or 2 in which n 'is l'ofifaiirwliich furtlier contain one or more fiber-reactive groupings. Heretofore and hereinafter, all rings shown in the formulas are aromatic.

The present invention also provides a process for preparing valuable new chromiferous, fiber-reactive azo dyestuffs which comprises condensing a chromium complex compound that comprises one atom of metal bound in complex union with a monoazo dyestuff molecule and with a disazo dyestuff molecule containing the grouping in which n=l or 2, and which comprises in addition an acylatable amino group, with an acylating agent that contains in addition to the acylating position a fiber-reactive grouping.

The parent chromium complex compounds of this invention may be prepared in the following manner:

1. A monoazo dyestuff of the formula (1) R,-N=NR in which R represents an aryl radical which carries a group capable of forming complexes in vicinal position to the azo bridge and R represents the residue of a coupling component that couples in vicinal position to a hydroxyl, keto or amino group, is chromed in the usual manner so that l lzl-chromium complex compound results which is then reacted with a disazo dyestuff containing the grouping (SOaH) where n is l or 2, which must additiona ly contain an acylatable amino group if the monoazo dyestufi' used does not contain such a group.

R, is preferably a residue of the benzene or naphthalene series, especially a carboxybenzene, hydroxybenzene or naphthol residue, which may contain a wide variety of substituents, for example, halogen atoms or nitro, alkyl, alkoxy and acylamino groups.

R may represent the residue of a phenolic, naphtholic or enolic coupling component or a naphthylamino residue.

The monoazo dyestuffs required for the manufacture of the metal compounds to be used in the present process may be prepared, for example, from the following diazo and coupling components; the diazo components are, of course, used in the form of diazonium salts.

Diazo Components 4- or 5-chloro-2-amino-loxybenzene, 4-, 5- or 6-nitro-2- amino- 1 -oxybenzene, 4,6-dichlro-2-amono- I -oxybenzene, 3,4,6-trichloro-2-amino-l-oxybenzene, 4-chloro-5- or -6- nitro-2-amino- 1 -oxybenzene, 4-nitro-6-chloro-2-amino- 1 -oxybenzene, 6-nitro-4-methyl-2-aminol -oxybenzene, 4-nitro-6- acetylamino-Z-amino-l-oxybenzene, 6-nitro-4-acetylamino-2- amino-l-oxybenzene, 4,6-dinitro-2-amino-l-oxybenzene, lamino-Z-oxynaphthalene, Z-aminobenzoic acid, 2- aminobenzene-lcarboxylic acid-4- or -5-sulfonic acid, 2- amino-l-oxybenzene-4- or -5-sulfonic acid, 4-chloroor 4- methyl-2-amino-l-oxybenzene-S- or -6-sulfonic acid, 6-nitro- Z-amino- 1 -oxybenzene-6-sulfonic acid, 6-nitro-2-aminol -oxybenzene-4-sulfonicacid and especially naphthalene compounds, for example, Z-amino-l-oxynaphthalene-4- or -8-sulfonic acid, 6-bromoor 6-methyl-l-amino-2-oxynaphthalene- 4-sulfonic acid and especially 1-amino-2-oxynaphthalene-4- sulfonic acid or 6-nitro-l-amino-2-oxynaphthalene-4-sulfonic acid, 4-chloroor 4-nitro-2-amino-l-oxybenzene--sulfonamide, 6-nitro-2-aminol -oxybenzene-4-sulfonamide, 2-aminol-oxybenzene-4- or -5-sulfonamide, 2-amino-l-oxybenzene-4- or -5-sulfonic acid phenylamide, 2-amino-l-oxybenzene-4- or -5-sulfonic acid monoor -dimethylamide, 4-methyl-2-aminol-oxybenzene-S-sulfonamide, 4-chloro-2-aminol -oxybenzine-Ssulfonic acid methyl-, -ethyl-, -isopropylamide, phenylamide, 4-chloro-2-aminol -hydroxybenzen e-S-sulfonyl-demethylamide, -diethylamide, -N-methyl-N-phenylamide, -N-methyl-N-B-hydroxyethylamide, -N-,B-hydroxyethyl- N-phenylamide or -N-ethyl-N--phenylamide and the corresponding compounds that contain instead of a sulfonamide group a methylsulfone group, an ethylsulfone group or especially a phenylsulfone group, a p-methylsulfone or pchlorophenylsulfone group. Coupling Components Oxybenzenes, for example, p-crcsol or p-tertiaryamyl phenol, 4-methyl-2-acetylaminol -oxybenzene, 4- acetylamino-l-oxybenzene, 4-(B-cyanethyU-phenene, ,B-keto carboxylic acid ester or amides, for example, acetoaceticacidanilide and l-acetoacetylamino-2-, -3- or -4- chlorobenzene, pyrazolones, for example, 1-phenyl-3-methyl- S-pyrazolone, l,3-diphenyl-5-pyrazolone, l'(2-, 3'- or 4'- chlorophenyl)-3-methyl-5-pyrazolone, l-(2-, 3'- or 4- methylphenyl )-3-methyl-5-pyrazolone, l-( 2 ,5 dichlorophenyl)-3-methyl-5-pyrazolone, l-(2-ethylor 4'- ethylphenyl)-3-methyl-5-pyrazolone, l-(napthyl-(l)- or (2))-3-methyl-5-pyrazolone, l-phenyl-5-pyrazolone-3-carboxylic acid phenyl amide, 1-n-octyl-3-methyl-5-pyrazolone, oxyquinolines, barbituric acid and napthylamines, for example, 6-bromo-, o-methoxyor 6-methyl-2-aminonaphthalene, 2-phenyl-aminonaphthalene, 2-aminonaphthalene itself and 2-amino-naphthalone-l-sulfonic acid, which is capable of coupling and, as is known, leads to dyestuffs similar to those produced with Z-aminonaphthalene with the separation of the SO -H group in the l-position, especially, however, naphtholes, for example, 6-bromoor 6-methoxy2-oxynaphthalene and especially l-acetylamino-7 -oxynaphthalene, l-n-butyryl-amino-7-oxynaphthalene, benzoylamino-7-oxynaphthalenc, l-carbethoxyamino-7oxynaphthalene, S-chlorol -oxynaphthalene, S-chlorol -oxynaphthalene, 5,8-dichloro-l-oxynaphthalene, 4,8- or 5,8- dichloro-Z-oxynaphthalene, 2-oxynaphthalene and, if desired, l-oxynaphthalene, l-phenyl-3-methyl-5-pyrazolone-2'-, -3- or -4'-sulfonic acid, 2'-chloro-l-phenyl-3-methyl-5- pyrazolone-4'- or -5-sulfonic acid, 2',5'-dichloro-l-phenyl-3- methyl-5-pyrazolone-4'- sulfonic acid, l(naphthyl-( l '))-3- methyl-5-pyrazolone-4', -5'-, -6-, -7- or -8'-sulfonic acid, 1- (naphthyl-(2))-3-methyl-5-pyrazolone-6'- or -8-sulfonic acid, l-acetoacetylamino-benzene-4-sulfonic acid and especially Z-aminoor 2-oxynaphthalene-4-, -5-, -6- or -7-sulfonic acid, l-oxynaphthalene-4-, -5- or -8-sulfonic acid, 2-phenylaminonaphthalene-3'- or -4'-sulfonic acid, l-phenyl-3-methyl- 5-pyrazolone-3-sulfonamide or -3'-sulfonic acid methyl amide, amides of 2-aminonaphthalene-4-, -5- or -6-sulfonic acid, of l-oxynaphthalene-4-, -5- or -8l-sulfonic acid or of 2- oxynaphthalene- 4-, -5-, -6- or 7-sulfonic acid, as well as coupling components containing amino groups, for example l-(3- or 4-amino-phenyl)- -3methyl-5-pyrazolone, 4-aminol-acetoacetylaminobenzene and especially amino naphthols, for example l-amino-8-hydroxynaphthalene-3,6- or -4,6- disulfonic acid, l-hydroxy-5-, -6- or -7-aminonaphthalene-3- sulfonic acid, l-amino-8-naphthol-4-sulfonic acid, aminobenzoyl-H- and -l(-acids.

The 1:1 complexes to be used in the process of the present invention may be obtained by reacting in an acidic medium a monoazo dyestuff which is free from complex-forming metal.

advantageously a dyestuff which contains a sulfonic acid group, with an excess of a salt of trivalent chromium, for example, chromium formate, chromium sulfate or chromium fluoride, at the boil or at a temperature above 100 C. For the conversion of the dyestuffs free from metal and containing sulfonic acid groups into the l:l-complexes it is in general advantageous to form the complexes in known manner, for example, in the presence of an organic solvent for example, an alcohol or fonnamide. Dealkylating formation of metal complexes is also suitable.

Generally, it is advantageous not to dry the parent dyestuff required for the formation of the lz2-complex after it has been manufactured and isolated but to use the dyestufi in the form of a moist paste.

The reaction of the lzl-metal complex with the metal-free disazo dyestuff is advantageously carried out in an aqueous, neutral to weakly alkaline medium under atmospheric or superatmospheric pressure, at room temperature or with heating, for example, at a temperature within the range of from 50 to l20 C. ln general, it is advantageous to use as equivalent proportions as possible of the metalliferous lzl-complex and of the metal-free disazo dyestuff for the reaction.

When the disazo dyestuff does not contain in the final component (designated as R, the following formula 2) amino or hydroxyl groups in ortho-position to the coupling position, the parent lz2-chromium complex, which according to this invention is condensed with an acylating agent that contains apart from the acylating position a fiber-reactive grouping, is also accessible by reaction of a lzl-chromium compound of the disazo dyestutf of the kind defined with a metal-free monoazo dyestuff of the kind defined.

Specially suitable disazo dyestuffs are those of the formula RPN=N (2) in which n is l or 2, R represents a be'hii rsi'difiiiicir contains a hydroxyl or carboxyl group in ortho-position to the azo bridge and R represents the residue of a coupling component which is able by the presence of a hydroxyl, keto or amino group, which is advantageously in vicinal position to the coupling position, to couple. Thus, R may be identical to R and R is in the first place a residue of the diazo components mentioned in defining the residue R,. R may represent the residue of a p-coupling amine, for example, aniline, toluidine, cresidine or one of the coupling components mentioned in defining the residue R As acylating agents, which according to this invention are to be coupled with the l:2-chromium mixed complexes containing an acylatable amino group, suitable aromatic halides (for example nitrochlorobenzene sulfonyl chloride or carboxylic acid chloride), for example, preferably aliphatic or heterocyclic acylating agents are suitable. From among the aliphatic acylating agents there may be specially named:

afi-dibromopropionic acid chloride or -bromide, chloroacetylchloride, B-chloropropionic acid chloride, aor B-bromacrylic acid chloride, acrylic acid chloride, chlorocrotonic acid chloride, propiolic acid chloride, chloromaleic acid anhydride, B-phenylsulfonylpropionic acid chloride, tetra-fiuorocyclobutane carboxylic acid chloride. It is advantageous to use heterocycles containing labile groups (for example sulfonyl groups) and/or halogen atoms bound, for example, to a heterocycle containing two or three nitrogen atoms as hetero atoms in a fiveor six-membered ring, or halides of aliphatic halogenated sulfonic or carboxylic acids. The following is an incomplete list of such acylating agents:

2-halogenobenzthiazoleor -oxazole carboxylic or sulfonic acid chloride, 4,5dichloro-l-phenylpyridazonecarboxylic or sulfonic acid chloride, 4,5-dichlorol -phenylpyridazonepropionic acid chloride, l,4-dichlorophthalazine carboxylic or sulfonic acid chloride, 2,3-dichloroquinoxaline carboxylic or sulfonic acid chloride, 2,4-dichloroquinoxaline carboxylic or sulfonic acid chloride, 2,4,6-trichloroor 2,46- tribromopyrimidine and their derivatives, which carry a cyano, nitro-, methyl-, ethyl-, carbamide-, sulfamide-, carbomethoxy-, carbalkoxy-, acyl- (for example, benzoyl-, acetylor propionyl-), alkenyl- (for example, allylor chlorvinyl-), or a substituted alkyl- (for example, carboxymethyl-, chloromethylor bromoethyl-) group in, for example, the 5- position. 2,4,5 ,-tetrachloroor 2,4,5,6- tetrabromopyrimidine, 2,6-dichloroor 2,6-dibromo-4-carboethoxypyrimidine, 2,4,5-trichloropyrimidine, 2,4- dichloropyrimidine-6-carboxylic acid chloride, 2 ,4- dichloropyrimidine-S-carboxylic acid chloride, 2 ,6-

dichloropyrimidine or 2,6-dibromopyrimidine-4- or -5-carboxylic acid amide, or -4- or -5-sulfonic acid amide, 2,4- dichloro-S-chloromethyl-6-methyl-pyrimidine, 2,4-dibromo- 5-bromomethyl--methylpyrimidine, 2,4-dichloro-5- chloromethylpyrimidine, 2,4-dibromo-5-bromomethylpyrimidine,2,5,6-trichloro-4-methylpyrimidine or 2,6- dichloro-4-trichloromethylpyrimidine, 4,6-dimethylsulfonyl- 2-chloro (or methylsulfonyl)-pyrimidine, 2,4-dichloro-5- methylsulfonyl-6-methylpyrimidine, 2,4,6-trichlorol ,3 ,5- triazine respectively 2,4,6-tribromo-1,3,5-triazine, dichloropyridazine-S-carboxylic. acid chloride, tetrachloropyridazine, and 4,6-dichloro-l,3,5-triazines substituted in position 2 by an aryl or alkyl group, for example, a phenyl, methyl or ethyl group, or by the residue of an aliphatic or aromatic mercapto compound linked through the sulfur atom or hydroxy compound linked through the oxygen atom, or especially by an -NH group or by the residue of an aliphatic, heterocyclic or aromatic amino compound linked through the nitrogen atom. As such compounds, whose residues may be linked in position two on the triazine nucleus by reaction with trihalogenotriazines, there may be mentioned, for example, the following:

aliphatic or aromatic mercaptoor hydroxyl compounds for example, thioalcohols, thioglycol acid, thiourea, thiophenol, methyl-, ethyl-, isopropyl alcohol, glycolic acid, phenol, chloroor nitrophenol, phenolcarboxylicand sulfonic acids, naphthols and naphtholsulfonic acids, especially however ammonia and acylatable amino groups including compounds, for example, hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulfonic acid, carbarmic acid and its derivatives, semiand thiosemicarbazides and -carbazones, methyl-, ethylisopropyl-, methoxyethyl-, methoxypropylamine, dimethyl-, diethyl-, methylphenyl-, ethylphenylamine, chlorethylamine, ethanol-amine, propanolamine, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic acid ester, aminoacetic acid ethylester, aminoethylsulfonic acid, N-methylaminoethylsulfonic acid, especially, however, aromatic amines, for example, aniline, N-methylaniline, toluidines, xylidines, chloroanilines por m-aminoacetanilide, nitroanilines, aminophenols, nitrotoluidines, phenylenediamines, toluylenediamines, anisidine, phenetidine, diphenylamine, naphthylamine, aminonaphthols, diaminonaphthalenes, and especially acidic groups containing anilines, for example, sulphanil-, metanil-, orthanilic acid, anilindisulphonic acid, anilin-w-methansulfonic acid, aminodibenzoic acid, naphthylaminomono-, diand trisulfonic acids, aminobenzoic acids, for example, 2-oxy-5- aminobenzoic acid, aminonaphtholmono-, and -diand -trisulfonic acids.

The triazine residues substituted in position 2 by the residue of a hydroxy, mercapto or amino compound or ammonia may be advantageously also introduced by first reacting the manufactured lz2-chromium complex compound with a 2,4,6- trihalogeno-l,3,5-triazine, especially cyanuric chloride, and then replacing one halogen atom in the resulting dihalogenotriazine residue(s) by reaction with one or several different of the compounds mentioned above.

Furthermore, in a dyestuff manufactured as described above, that contains a B-chloropropionyl, a,/3-dichloropropionyl or -dibromopropionyl residue, such a residue may subsequently be converted according to this invention into an unsaturated acyl radical, for example, an acryl, a chloroacryl or bromoacryl group, by dehydrohalogenation with an alkaline agent. 2. According to a variation of the present process for the manufacture of the new chromiferous, fiber-reactive azo dyestuffs, the lzl-chromium complex of the monoazo dyestuff is acylated with one of the aforementioned acylating agents and then reacted with the disazo dyestuff. According to another variation the disazo dyestuff molecule may first be condensed with one of the aforementioned acylating agents and then converted into the lz2-chromium complex compound of this invention with the lzl-chromium complex of the monoazo dyestuff.

The new chromiferous, reactive, mixed complexes obtained by the present process and its variants, are suitable for dyeing or printing a wide variety of materials, for example, silk, wool, superpolyamide fibers, and more especially polyhydroxylated materials of fibrous structure, including both synthetic fibers, for example, of regenerated cellulose or viscose fibers, and natural materials, for example, linen and especially cotton.

Many of these dyestuffs display even in a weakly acidic to acidic bath a high affinity for the said nitrogenous materials so that they deposit well on them. The resulting dyeings, especially those on wool, are even and are distinguished by their good fastness to light, washing, fulling, decatizing, carbonizing and abrasion.

Suitable cellulose dyestuffs are especially those dyestuffs which contain in every dyestuff molecule two to four sulfo groups; they are suitable for dyeing cellulose by the direct dyeing method from a dilute dyebath or by padding by the socalled pad dyeing method, according to which the cellulose is impregnated with an aqueous, if desired, salted, dyestuff solution and the dyestuffs are fixed on the material by an alkali treatment, preferably at an elevated temperature. This process furnishes dyeings that are as a rule distinguished by good fastness to light, and especially excellent wet fastness properties.

When cellulose fibers are printed, valuable, fast prints are also obtained when the dyestuffs are fixed on the material by a heat treatment in the presence of, for example, sodium bicarbonate, potassium carbonate or an alkali hydroxide solution.

Compared with the known manufacturing processes the present process is further distinguished by the fact that it produces dyestuffs of remarkable chemical uniformity and by their valuable neutral grey and black tints.

It is advantageous to remove after dyeing or printing any unfixed dyestuff as completely as possible. For this purpose the dyeing or prints are thoroughly rinsed in warm and cold water and then soaped in the presence of a nonionic dispersant and/or wetting agent, or they may be neutralized by addition of ammonia.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages in the following examples are by weight.

EXAMPLE 1 47.35 parts of the monoazo dyestuff obtained by alkaline coupling of l-amino-8-hydroxynaphthalene-3,6disulfonic acid with diazotized l-hydroxy-2-amino-4-chlorobenzene in the usual manner are stirred with 500 parts by volume of water and 10 parts by volume of 30 percent sodium hydroxide solution. The resulting solution is mixed with 25 parts by volume of a 4N-sodium nitrite solution and then dropped into a mixture of of parts by volume of 36 percent hydrochloric acid, I parts by volume of water and 200 parts of ground ice during one hour. The resulting suspension is further stirred for 2 hours at 0 to 5 C., freed from a slight excess of nitrous acid, which might be present, by addition of sulfamic acid, and then stirred into a solution of 15 parts of 2-hydroxy-naphthalene and 70 parts of anhydrous sodium carbonate in 300 parts by volume of water, 200 parts of ice and parts by volume of a 30 percent sodium hydroxide solution.

When the coupling is completed, the completely precipitated disazo dyestuff is filtered off, washed with dilute sodium chloride solution and expressed. The paste (corresponding to 62.85 parts of the above disazo dyestuff) and 52.35 parts of the l:l-chromium complex of the monoazo dyestuff which can be obtained by a method known per se from diazotized l-hydroxy-2-amino-4-chlorobenzene and lamino-8-hydroxynaphthalene-3,-disulfonic acid are stirred with 750 parts of water of 60 C. The pH is adjusted to a steady value of 9 by dropping in a dilute sodium hydroxide solution and the mixture is stirred and heated to to C. When neither of the two starting components can be identified in the resulting clear solution, the whole is cooled to 0 to 3 C. and neutralized with dilute hydrochloric acid. Then a solution of 27.5 parts of a,B-dibromopropionylchloride in parts by volume of acetone is dropped in with vigorous stirring and while cooling in an ice bath, and by simultaneous addition of dilute sodium hydroxide solution the mixture is maintained at a pH value of 6 to 7. When diazotizable amino groups can no longer be identified in the deep black, clear reaction solution, the dyestuff is precipitated by adding potassium chloride, filtered off, washed with concentrated potassium chloride solution and dried under vacuum at 60 C.

The new dyestuff is obtained in form of a very readily watersoluble dark powder; it dyes wool in the presence of ethylene adducts with higher alcohols or amines, full grey-violet to black tints.

EXAMPLE 2 A solution, prepared as described in example 1, of the uniform mixed complex acylated with a,/3-dibromopropionylchloride is mixed with 10 parts by volume of 30 percent sodium hydroxide solution while maintaining a temperature of 15 C. and stirred for 15 minutes at a pH value of 12. The deep black solution is then neutralized with dilute hydrochloric acid, and the dyestuff is precipitated with potassium chloride, filtered off and dried under vacuum at 60 C.

The resulting dyestuff is readily soluble in water, and its tinctorial behavior is similar to that of the dyestuff described in example 1.

EXAMPLE 3 48.4 parts of the monoazo dyestuff obtained by a method per se by alkaline coupling of l-amino-B-hydroxynaphthalene- 3,6disulfonic acid with diazotized l-hydroxy-2-amino-4- nitrobenzene are stirred with 500 parts by volume of water and 10 parts by volume of 30 percent sodium hydroxide solution. The resulting solution is mixed with 25 parts by volume of a 4N-sodium nitrite solution and within l hour dropped into a mixture of 70 parts by volume of 36 percent hydrochloric acid, 100 parts by volume of water and 200 parts of ground ice. The resulting suspension is stirred. for 2 hours at 0 to 5 C., freed from a slight excess of nitrous acid with sulfamic acid, and the whole is then stirred into a solution of 15 parts of Z-hydroxynaphthalene and 70 parts of anhydrous sodium carbonate in 300 parts by volume of water, 200 parts of ice and 10 parts by volume of 30 percent sodium hydroxide solution. When the coupling is completed, the quantitatively precipitated disazo dyestuff is filtered off, washed with dilute sodium chloride solution and expressed.

The paste (corresponding to 63.9 parts of the above disazo dyestuff) and 52.35 parts of the lzl-chromiurn complex, prepared by a method known per se, of the monoazo dyestuff from diazotized lrhydroxy-2-amino-4-chlorobenzene and lamino-8-hydroxynaphthalene-3,6-disulfonic acid are stirred with 750 parts of volume of water of 60 C. The pH is adjusted to a constant value of 9 by dropping in a dilute sodium hydroxide solution and the mixture is then heated to 90 to 95 C. while being stirred. When no starting component can be identified in the resulting clear solution, it is cooled to 0 to 3 C. and neutralized with dilute hydrochloric acid. Then a solution of 19 parts of cyanuric chloride in 100 parts by volume of acetone is added and the whole stirred on for some hours at to C., while maintaining a constant pH value below 7 by dropping in dilute sodium hydroxide solution. When diazotizable amino groups can no longer be identified in the clear solucooled to 0 to 5 C. and a solution of 19 parts of cyanuric chloride in 100 parts by volume of acetone is added. During a few hours at 0 to 5 C. sufficient sodium hydroxide solution is stirred in dropwise to maintain the pH value of the solution Cl. SOaH tion, a neutral solution of 19 parts of l-aminobenzene-Ii-sul- 5 constant below 7. When diazotizable amino groups can no fonic acid in 500 parts of water is added and the batch heated longer be identified, a neutral solution of 19 parts of lto 35 to 40 C. and stirred for a few hours at this temperature aminobenzene-3-sulfonic acid in 500 parts of water is added while maintaining the pH value at 6.0 to 7 by dropping in more and the mixture heated to 35 to 40 C., then heated for a few dilute sodium hydroxide solution. hours longer at this temperature while maintaining its pH When sodium hydroxide solution is no longer being con- 10 value at 6.0 to 7 by dropping in more of the dilute sodium sumed, the dyestuff is salted out with potassium chloride, filhydroxide solution, until sodium hydroxide is no longer being tered, washed with concentrated potassium chloride solution consumed. and dried at 50 C., whereupon the new dyestufi' is obtained in The paste of the above-mentioned disazo dyestuff is stirred form of a dark powder which readily forms a blue-black soluinto the resulting solution of the lzl-chromium complex, and tion in water. It dyes cellulosic materials by the dyeing method the mixture is stirred at 35 to 40 C. until neither of the two described very fast, deep black tints. parent components can be identified. At the same time the pH value of the resulting solution is maintained at 7 by dropping EXAMPLE 4 in dilute sodium hydroxide solution.

The deep-green solution of the unitary mixed complex Parts of the fnonoazo dyestuff Obtameq m the usual dyestuff is then cooled to 0 to 5 c. and acylated with afimanne' y alkalme coupling of y dibromopropionylchloride as described in example 2. When y p h e e- ,fii c acid with dialotiled 1-hy ydiazotizable amino groups can no longer be identified in the amino'4'nitl'obenlene are dialotized as described in example resulting greenish black reaction solution, the dyestuff is The suspension of the dial) compound is Stirred dropwise salted out with potassium chloride, filtered off, washed with imo 3 Solution, Cooled 8! of 19 Parts of concentrated potassium chloride solution and dried under 'aminophenyl)-3-methyl-5-pyrazolone and 80 parts of anvacuum at 50 C,

hydrous sodium carbonate in 300 parts by volume of water Th new dye t fi i btained as a dark owder; it is very and 5 parts by volume of a percent solution of sodium readily soluble in water and produces on cotton and wool by hydroxide. When the coupling is completed, the completely 30 the dyeing methods described above olive-grey tints having precipitated disazo dyestufi is filtered off, washed with dilute very good fastness properties. sodium chloride solution and e pressed. The following table contains further examples of similar 52- p ts f t um c p p ep y a mixed complexes accessible from the lzl-chromium complex method known P $6,0f the mOflflZO dyestuff from ilc of the dyestuff listed in column I and the corresponding lhydroxy-Z-amino-4-chlorobenzene and l-amino-B-hydrox- 3 5 dyestuff in column I] by acetylating the compound in column ynaphthalene-3,6-disulfonic acid are dissolved at room temill. The tint obtained on cotton or wool with the mixed comperature in l,000 parts by volume of water. The batch is then plex is shown in each casein column IV.

I II III IV shade I I I n W V 7 V I H u ir Acrylic acid chloridcun Grey- (|)H OII IIIHZ C O OH OH N=N N=N- -N=N HO;S SO lI HO3S- SOKH ]I O a-Bromacrylie acid ])0.

| chlor e. (|)H (|)H ITIHZ (DH (Ell IIN'ZN N=N N=N HO3S S 03H HO3S -S 03H Cl N 0? Same as above ame a above 2,4,5,6-tetrachloro- D0.

d V V W V W pyrimidine.

HO Chloroacetylchloride Violet-grey. 1

0H 0H NH:

I II III IV 511 adc HCI) l .do Bluish-dark green. (IJH (|)H NH; (RI (|)H N:N- CH3 -N= N=N O- H038 303 HOaS -S0:

N0 N O 2 Same as above .A Same a above Cyanidechlorlde D0.

D0 OII Cl fl-Chloropropiouyl- Grey.

I chloride. R I fi H0 S- -s 03H 01 N Oz Do. II N afi-Dibromopropionw- Grcenish grey.

l chloride. (|)H (|)H l ll- '--N- Do. H0 chloroacetylchloridcnn Roddishgrcy.

(])H ?H I II=N* H O S- S 0 H D0 Same a above Dibrompropionic acid Reddish-gr ychloride.

D0 l H(|) Acrylic acid chloride. Violet-grey.

a 1 H O D0 Same as above a-Bromacrylic acid 0- bromide.

D0 H 0 Dibromopropionic acid Reddish-grey.

I chloride. (RH OH 1TT=N H 0 8- S 0 H H OH NH Same as above Dibromopropionyl- Bluish-grey- I I chloride.

N 0: H 035- S 03H D0 do Acrylic acid chloridem. Do.

I II III IV shade D HO fl-Bromoaerylic acid Black.

| chlor' c. r i= H 03 S N O; S 03H HO OH H O NH? (i-metnoxy-2,4-dichlor0' D0.

l l triazinc.

OH H O N: -N=N- I l N=N- H 03 S S 03H N O? H 03 s s 03H Same as above H O a,-BD1bron1opropionic Do.

| acid chloride.

OH H (I) I\|I=N U O J\ OzN H 0: s s 0 11 ()H H O NH; H (I) Acrylic acid ch1oridc Do. N=N;O\/j m H 0 I |I=N 0 N N=N H 03 s 03H i H 03 S/ S 03H C| H H(|) H (l) Chloroacetylchlmidc. Brown-black.

II 03 S N=N |OH H O I\|I:N-

H 03 S NH; N 02 H 03 S s 03H OH HO NH; Same a above a,B-Dibr0m0 roplonic Bl ck- I l 1 acid ehlori e.

H O: S S 03H N 02 D0 d0 6-methoxy2A-dichloro D triazine.

Dyeing Instruction (wool) 60 The resulting reaction product gives a substantially clear solu- 100 parts of knitting wool are immersed at 50 to 80 C. in a tion in water. dyebath containing in 3,000 parts of water 10 parts of crystal- Pad Dyeing Method and Fixing on Cellulose With Dry Heat line sodium sulfate, 6 pans of percent acetic acid, 0.5 part 3 parts of dyestufi', 2 parts of sodium carbonate (or 3 parts of the adduct of oleylamine and ethylene oxide described of sodium bicarbonate) and 25 parts of urea are dissolved in under A, and 2 parts of the dyestuff described in example I. parts of water, and this solution is used for impregnating a The dyebath is heated to the boil during half an hour and dye cotton fabric which is then expressed to a weight increase of ing is performed for 1 hour at the boil. The wool is then rinsed 75 percent and dried at C. The fabric is then exposed to and dried. A level grey dyeing is obtained. dry heat of 140 C. for about 5 minutes, rinsed and soaped at Manufacture of the Ethylene Oxide Adduct the boil. The dyeing obtained is fast to washing at the boil.

I00 parts of commercial oleylamine are mixed with 1 part 70 Printing instruction of finely divided sodium and heated to 140 C., whereupon A solution of 10 parts of dyestufi and 30 parts of urea in 54 ethylene oxide is introduced at 135 to 140 C. When ethylene parts of water is stirred into parts of a 5 percent sodium aloxide is being consumed rapidly, the reaction temperature is ginate thickening and 6 parts of sodium bicarbonate are lowered to to C. and the introduction of ethylene 75 added. A cotton fabric is printed with the resulting printing oxide is continued until 1 l3 parts thereof have been absorbed.

paste in the usual manner, then dried and treated for 8 minutes with saturated steam at 100 C. After rinsing in cold and hot water a deep black print is obtained which has been fixed so as to make it fast to washing at the boil.

We claim:

I. A fiber-reactive 1:2-chromium complex compound wherein the chromium atom is bound to one molecule of a monoazo compound of the formula R,N=N--R and one molecule of a disazo compound of the formula HO N=NR1 in which R, is unsubstituted or substituted hydroxy benzene or naphthalene wherein hydroxy is in a position vicinal to azo, and substituents are members selected from the group consisting of chloro, nitro and sulfo; R is (a) unsubstituted or substituted hydroxy or amino naphthalene wherein hydroxy or amino are in a position vicinal to the azo bridge and substituents are members selected from the group consisting of amino and sulfo, (b) l-phenyl-3-methyl-5-pyrazolone linked in the four-position with the azo bridge or (c) aceto acetylaminophenyl linked in a position vicinal to the keto group with the azo bridge; n is l to 2; R is unsubstituted or substituted hydroxy or carboxy benzene wherein hydroxy or carboxy are in the ortho position to the azo bridge and substituents are members selected from the group consisting of chloro and nitro; and R is unsubstituted or substituted amino or hydroxy naphthalene wherein amino or hydroxy are in a position vicinal to the azo bridge and substituents are members selected from the group consisting of chloro, amino and sulfo, (d) unsubstituted or substituted l-phenyl-3-methyl-5- pyrazolone linked in four-position with the azo bridge and wherein the phenyl substituent is amino, or (e) acetyacetylaminophenyl linked in a position vicinal to the keto group, and wherein said 1:2-chromium complex is bonded by one to two fiber-reactive aliphatic, saturated or unsaturated carboxylic acids containing two to three carbon atoms and substituted by one to two chlorine or bromine atoms, chloroor bromo-pyrimidines or chloroor bromo-triazines.

2. A fiber-reactive 1:2-chromium complex compound as claimed in claim I, in which R. represents the radical 3. A fiber-reactive 1:2-chromium complex compound as claimed in claim 1 in which the chromium atom is bound to a monoazo dyestuff of the formula blIH-- S wherein Y is chlorine or N and Z the radical of an aliphatic saturated or unsaturated carbocyclic acid which contains two to three carbon atoms and one to two chlorine or bromine atoms, and which is bound to the NH--bridge through its CO-group.

4. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula 5. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula 6. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula 7. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formulas OH HO NHCOCH2C1 OH OH I I I 3 N=N H03 s N=N l H03 S S 03H 5 CH3 N O 2 l I O 2 and W Y f 7 OH Y and I 10 OH OH HO N:N-- CH3 N-ONH-CO-(hCHz OH OH N=N- I Br N=N- I O-\ I N N=N Ha S 0311 1 5 l 31033 S 0511 N02 i N 2 8. The eomblex ehromi u l n Eolfibhlfillhi'flniins one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formulas 

2. A fiber-reactive 1:2-chromium complex compound as claimed in claim 1, in which R4 represents the radical
 3. A fiber-reactive 1:2-chromium complex compound as claimed in claim 1, in which the chromium atom is bound to a monoazo dyestuff of the formula wherein Y is chlorine or NO2 and Z the radical of an aliphatic saturated or unsaturated carbocyclic acid which contains two to three carbon atoms and one to two chlorine or bromine atoms, and which is bound to the NH-bridge through its CO-group.
 4. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula
 5. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula
 6. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formula
 7. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formulas
 8. The complex chromium compound which contains one atom of chromium in complex combination with one molecule of each of the two dyestuffs of the formulas 